Chemical binding of renewable oils to polyester emulsion

ABSTRACT

Methods for making toner particles comprising a polyester-wax resin, wherein the polyester-wax resin includes a bio-based oil that is chemically incorporated into the main chain of the polyester resin. The toner particles may be formed using emulsion aggregation methods. A toner formed from the toner particles may be used in low-oil or oil-less fusing systems.

This application is a divisional application of U.S. patent applicationSer. No. 13/559,928 filed Jul. 27, 2012, the entire disclosure of whichis incorporated herein by reference.

TECHNICAL FIELD

Disclosed herein is a method for forming a polyester emulsion, a methodfor forming a toner particle, and toner particles formed from thatmethod.

BACKGROUND

Emulsion aggregation (EA) is a method for preparing toners. EAtechniques involve forming an emulsion latex of resin particles byheating the resin using a batch or semi-continuous emulsionpolymerization, as disclosed in, for example, U.S. Pat. No. 5,853,943,the disclosure of which is hereby incorporated by reference in itsentirety. Other examples of emulsion/aggregation/coalescing methods forpreparing toners are illustrated in U.S. Pat. Nos. 5,902,710; 5,910,387;5,916,725; 5,919,595; 5,925,488, 5,977,210, 5,994,020, and U.S. PatentApplication Publication No. 2008/0107989, the disclosures of each ofwhich are hereby incorporated by reference in their entirety.

EA toners are sometimes used in forming print and/or xerographic images.Polyester EA ultra low melt (ULM) toners have been prepared utilizingamorphous and crystalline polyester resins as illustrated, for example,in U.S. Patent Application Publication No. 2008/0153027, the disclosureof which is hereby incorporated by reference in its entirety.Incorporating these polyesters into the toner generally requires thatthe polyesters first be formulated into latex emulsions prepared bysolvent containing batch methods, for example solvent flashemulsification and/or solvent-based phase inversion emulsification(PIE).

Oils or waxes are sometimes used to aid in toner release during fusing,and to prevent the fused image document from curling around the fuserroll. However, using oils in a fusing system may cause differentialgloss due to oil remaining on the surface of fused prints. A low-oil, oroil-less, fuser system may alleviate issues such as caused bytoner-fuser oil interactions, oil contamination, and the like.

A wax may be necessary for a low-oil fuser to function. Waxes aid inpreventing document offset, which may occur where fused images becometransferred from one document to another (toner-to-toner andtoner-to-paper) over a prolonged period of time or at elevatedtemperatures. In addition, waxes may be added to toner formulations toreduce stripper finger marks, such as scratch marks and changes in imagegloss, on the fused images.

Wax is typically added up front with pigment and polyester latex in EAtoner methods as a separate, aqueous emulsion. The wax emulsion mixesand aggregates throughout the toner particle formation step. When addedas a separate entity during aggregation and coalescence of tonerparticles, the wax may be rejected by the emulsion or may beincompatible with other toner components. In addition, adding a wax as aseparate entity may result in uneven distribution of wax domainsthroughout toner particles and high wax content on particle surface.

Adding a wax as part of the polyester resin may avoid the separateemulsification step of the bio-based oil and, thus, may reduce the costof EA toner.

U.S. Patent Application Publication No. 2011/0129774, now abandoned,discloses incorporating an oil component directly into the polyesterduring the phase inversion emulsification (PIE) stage. However, the oilcomponent in that application was not bonded chemically to the resin,and no covalent bonds were formed. Instead, the oil component wasphysically trapped inside the core of the latex aggregates. Thus, theoil may flow out of the core making it difficult to control the domainsof the wax, or control how the wax is dispersed throughout the toner.Accordingly, a need exists for a method of chemically incorporating awax into the main chain of a polyester.

SUMMARY

Described in embodiments is a method including the steps of forming apolyester-wax resin emulsion by epoxidizing unsaturated units of apolyester resin, synthesizing an amino-functionalized bio-based oil, andchemically bonding the amino-functionalized bio-based oil to theepoxidized units of the polyester resin; forming a pre-toner mixturecomprising the polyester-wax resin emulsion; and aggregating andcoalescing the pre-toner mixture to form the toner particles.

Toner particles comprising a polyester-wax resin made according tomethods described herein may be used in an oil-less fusing fixture,without adversely affecting the xerographic device. Chemicallyincorporating the wax into the resin may eliminate the need for aseparate wax emulsification step, may avoid wax rejection during theaggregation/coalescing method, and may provide better control overdomains of the wax and over how the wax is dispersed throughout thetoner.

EMBODIMENTS

Methods of making toner particles are described herein, wherein thetoner particles may comprise a polyester-wax resin, and the bio-basedoil may be a bio-based oil that is chemically incorporated into the mainchain of the polyester resin. The toner particles may further include acolorant and other conventional toner additives.

Embodiments provide a unique method of chemically attaching a liquidbio-based oil such as, for example, jojoba oil, to a polyester chain.The resulting polyester-wax resin includes a bio-based oil that ischemically incorporated into the main chain of the polyester resin, suchas a pendent molecule. The method disclosed herein includes epoxidizinga vinyl functional group in a polyester resin, synthesizing aminoderivatives of the bio-based oil, and covalently attaching the polyesterresin to the amino derivatives of the bio-based oil.

A bio-based oil incorporated into the main chain of a polyester mayallow for a toner to be made without the use of an external or secondwax emulsion, while allowing the toner to be capable of use in low-oilor oil-less fusing systems. By omitting the second or separate waxemulsion, the cost and time necessary for forming the toner particles isdecreased. Further, as compared to physically incorporating a bio-basedoil into a polyester resin, a bio-based oil chemically incorporated intothe main chain of a polyester may be more intact within the tonerparticle and less likely to flow to the surface of the toner particle.

As discussed above, this resin design allows for a toner method thatdoes not include a second or separate wax emulsion and also provides theuse of oil-less fusing or low-oil fusing system. From an environmentalperspective, omitting any external or second wax emulsion may limit theamount of surfactants or organic solvents used as compared toconventional methods not using the polyester-wax resin disclosed herein.

The polyester-wax resin may have an acid value ranging from about 5 toabout 40, or from about 10 to about 35, or from about 15 to about 30,depending on the degree of polymerization and the overall stoichiometryof the diol to diacid monomers ratio. If the polyester-wax resin has anexcess diacid monomer ratio, the resin will have high acid values.However, if the diol monomer is used in excess, then the acid value willbe low, such as about 5. The functionality of the wax (whether itincludes an acidic group or a hydroxyl group) will only be part of theoverall monomers used in making the resin.

The polyester-wax resin may be obtained through the condensation of adiol, a diacid, and a bio-based oil comprised of one or two functionalgroups either or both being a carboxylic acid group or hydroxyl group.The bio-based oil is chemically bound through esterification to thepolyester resin on the main chain of the polymer, including the end unitof the polymer. As explained above, any wax is suitable for use inderiving the polyester-wax resin described herein so long as it has oneor two functional groups, that is, the wax may have one hydroxylfunctional end group, one acidic functional end group, two hydroxylfunctional end groups, two acidic functional end groups, or one hydroxylfunctional end group and one acidic functional end group.

Bio-Based Oil

In embodiments, a bio-based oil is added to a polyester resin to form apolyester-wax resin. A phase inversion method may be used to incorporatethe bio-based oil in the core of the polyester resin, such as a latexresin.

The bio-based oil may include hydrogenated and non-hydrogenatedvegetable oils extracted from plants such as, for example, jojoba oil,coconut oil, corn oil, cottonseed oil, olive oil, palm oil, palm kerneloil, rapeseed oil, almond oil, cashew oil, hazelnut oil, peanut oil,macadamia oil, mongongo oil, pine nut oil, pistachio oil, walnut oil,bottle gourd oil, buffalo gourd oil, pumpkin seed oil, watermelon seedoil, acai oil, blackcurrant seed oil, borage seed oil, evening primroseoil, carob pod oil, amaranth oil, apricot oil, apple seed oil, arganoil, artichoke oil, avocado oil, babassu oil, ben oil, borneo tallow nutoil, cape chestnut oil, cocoa butter, algaroba oil, cocklebur oil,poppyseed oil, cohune oil, dika oil, false flax oil, flax seed oil,soybean oil, sunflower oil, grape seed oil, hemp oil, kapok seed oil,lallemantia oil, marula oil, meadowfoam seed oil, mustard oil, nutmegbutter, nutmeg oil, okra seed oil, papaya seed oil, perilla seed oil,pequi oil, pine nut oil, poppyseed oil, prune kernel oil, quinoa oil,ramtil oil, rice bran oil, royle oil, sacha inchi oil, camellia oil,thistle oil, tomato seed oil, wheat germ oil, tung oil, linseed oil,safflower oil, sesame oil, combinations thereof, and the like.

The bio-based oil may include eicosenoic acids and alcohols, such aseicosenol and docosenol. The eicosenoic acids and alcohols may bepresent in the bio-based oil in an amount of from about 1 to 30% byweight of the bio-based oil, such as from 2 to 15% by weight of thebio-based oil, or from about 3 to 10% by weight of the bio-based oil.

In embodiments, a natural-based, environmentally friendly jojoba oil(obtained from Simmondsia chinensis; commercially available from SigmaAldrich) may be utilized as the bio-based oil. The jojoba oil may bepartially hydrogenated and/or isomerized, and includes long chain estershaving mainly 40-42 carbon atoms where the carboxy-esteric group iscontained within the high lipophilic chain.

In embodiments, synthetically made jojoba oil may be used and includes amixture of esters of long chain monounsaturated acids and alcoholshaving 16-26 carbon atoms, e.g. esters of oleic acid and erucic acidwith oleic alcohol or erucyl alcohol. Jojoba oil is stable toward oxygenand high temperatures due to its chemical structure, and it is lessreactive when compared with other olefins. Additionally, oxidation atthe allylic position is very slow or not existent, so it is a goodcandidate as a release aid in toner formulations.

In embodiments, the bio-based oil is present in an amount of from about0.1% by weight to about 25% by weight of the total toner particle, suchas from about 1% by weight to about 15% by weight, such as from about 2%by weight to about 10% by weight. In addition, the bio-based oil may bepresent in the polyester-wax resin in an amount of from about 1 weightpercent to about 20 weight percent of the total resin, such as fromabout 3 weight percent to about 18 weight percent, or from about 5weight percent to about 15 weight percent of the total resin.

In embodiments, the bio-based oil may be in the form of oil droplets.Without any type of mixing, shaking, and the like, the oil droplets mayhave a size of from about 0.5 μm to about 500 μm in diameter, such asfrom about 1 μm to about 250 μm in diameter, or from about 10 μm toabout 60 μm in diameter.

Polyester Resin

The polyester resin of the polyester-wax resin may be synthesized tohave high acid numbers, such as high carboxylic acid numbers, of, forexample, 40 mg/eq. KOH. For example, if the polyester-wax resin formedaccording to the methods described herein is to be used to form tonerparticles by an emulsion aggregation method, then the polyester resinand resulting polyester-wax resin may have a high acid number of, forexample, from about 5 mg/eq. KOH to about 40 mg/eq. KOH, such as fromabout 10 mg/eq. KOH to about 30 mg/eq. KOH, or from about 13 mg/eq. KOHto about 22 mg/eq. KOH.

The polyester resin may be a polyester resin made to have a high acidnumber by using an excess amount of diacid monomer to the diol monomer,or by using acid anhydrides to convert the hydroxl ends to acidic ends,for example, by reaction of the polyester resin with known organicanhydrides such as trimellitic anhydride, phthalic anhydride, dodecylsuccinic anhydride, maleic anhydride, 1,2,4,5-benzenedianhydride.5-(2,5-dioxotetrahydrol)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride,5-(2,5-dioxotetrahydrol)-4-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, pyromellitic dianhydride, benzophenone dianhydride, biphenyldianhydride, bicyclo[2,2,2]-oct-7-ene tetracarboxylic acid dianhydride,cis,cis,cis,cis,1,2,3,4-cyclopentane tetracarboxylic acid dianhydride,ethylenediamine tetracetic acid dianhydride, 4,4′-oxydiphthalicanhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride,ethylene glycol bis-(anhydro-trimellitate), propylene glycolbis-(anhydro-trimellitate), diethylene glycolbis-(anhydro-trimellitate), dipropylene glycolbis-(anhydro-trimellitate), triethylene glycolbis-(anhydro-trimellitate), tripropylene glycolbis-(anhydro-trimellitate), tetraethylene glycolbis-(anhydro-trimellitate), glycerol bis-(anhydro-trimellitate), andmixtures thereof.

A hydroxyl-terminated polyester resin may be converted to a high acidnumber polyester by reacting the hydroxyl-terminated polyester withmultivalent polyacids, such as 1,2,4-benzene-tricarboxylic acid,1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylicacid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylicacid, 1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane,tetra(methylene-carboxyl)methane, and 1,2,7,8-octanetetraearboxylicacid; acid anhydrides of multivalent polyacids; and lower alkyl estersof multivalent polyacids; multivalent polyols, such as sorbitol,1,2,3,6-hexanetetrol, 1,4-sorbitane, pentaerythritol, dipentaerythritol,tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol,glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol,trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene,mixtures thereof, and the like.

In embodiments, the polyester resin may be, for example,poly(1,2-propylene-diethylene)terephthalte, polyethylene-terephthalate,polypropylene-terephthalate, polybutylene-terephthalate,polypentylene-terephthalate, polyhexylene-terephthalate,polyheptadene-terephthalate, polyoctalene-terephthalate,polyethylene-sebacate, polypropylene-sebacate, polybutylene-sebacate,polyethylene-adipate, polypropylene-adipate, polybutylene-adipate,polypentylene-adipate, polyhexylene-adipate polyheptadene-adipate,polyoctalene-adipate, polyethylene-glutarate, polypropylene-glutarate,polybutylene-glutarate, polypentylene-glutarate, polyhexylene-glutarate,polyheptadene-glutarate, polyoctalene-glutarate, polyethylene-pimelate,polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate,polyhexylene-pimelate, polyheptadene-pimelate, poly(propoxylatedbisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate),poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylatedbisphenol co-ethoxylated bisphenol co-fumarate), poly(1,2-propylenefumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylatedbisphenol co-maleate), poly(butyloxylated bisphenol co-maleate),poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate),poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate),poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenolco-itaconate), poly(co-propoxylated bisphenol co-ethoxylated bisphenolco-itaconate), poly(1,2-propylene itaconate), or mixtures thereof.

In embodiments, if the polyester-wax resin is to be used in a UV curabletoner, then the polyester resin of the polyester-wax resin may be anunsaturated polyester. Unsaturated polyester resins may include any ofvarious polyesters, such as SPAR™ (Dixie Chemicals), BECKOSOL™(Reichhold Inc), ARAKOTE™ (Ciba-Geigy Corporation), HETRON™ (AshlandChemical), PARAPLEX™ (Rohm & Hass), POLYLITE™ (Reichhold Inc),PLASTHALL™ (Rohm & Hass), CYGAL™ (American Cyanamide), ARMCO™ (ArmcoComposites), ARPOL™ (Ashland Chemical), CELANEX™ (Celanese Eng), RYNITE™(DuPont), STYPOL™ (Freeman Chemical Corporation), XP777 (ReichholdInc.), mixtures thereof, and the like. The polyester resin may also be afunctionalized polyester, such as carboxylated, sulfonated, or the like.A sodio sulfonated polyester may be used.

Embodiments may include a crystalline polyester resin. As used herein,“crystalline” refers to a polymer with a three dimensional order.“Semicrystalline” as used herein refers to materials with a crystallinepercentage of, for example, from about 10 to about 60 percent, and morespecifically from about 12 to about 50 percent. Further, as usedhereinafter “crystalline” encompasses both crystalline resins andsemicrystalline materials, including saturated and unsaturatedcrystalline materials, unless otherwise specified. Alkali sulfonatedpolyester resins may be used.

Crystalline polyester resins may include, but are not limited to, alkalicopoly(5-sulfoisophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfoisophthaloyl)-copoly(propylene-adipate), alkalicopoly(5-sulfoisophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly (propylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(propylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylenes-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(propylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(propylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate),poly(octylene-adipate), and combination thereof, and wherein the alkalimay be a metal such as sodium, lithium, or potassium.

Semicrystalline polyester resins may include, for example,poly(3-methyl-1-butene), poly(hexamethylene carbonate),poly(ethylene-p-carboxy phenoxy-butyrate), poly(ethylene-vinyl acetate),poly(docosyl acrylate), poly(dodecyl acrylate), poly(octadecylacrylate), poly(octadecyl methacrylate), poly(behenylpolyethoxyethylmethacrylate), poly(ethylene adipate), poly(decamethylene adipate),poly(decamethylene azelaate), poly(hexamethylene oxalate),poly(decamethylene oxalate), poly(ethylene oxide), poly(propyleneoxide), poly(butadiene oxide), poly(decamethylene oxide),poly(decamethylene sulfide), poly(decamethylene disulfide),poly(ethylene sebacate), poly(decamethylene sebacate), poly(ethylenesuberate), poly(decamethylene succinate), poly(eicosamethylenemalonate), poly(ethylene-p-carboxy phenoxy-undecanoate), poly(ethylenedithionesophthalate), poly(methyl ethylene terephthalate),poly(ethylene-p-carboxy phenoxy-valerate),poly(hexamethylene-4,4′-oxydibenzoate), poly(10-hydroxy capric acid),poly(isophthalaldehyde), poly(octamethylene dodecanedioate),poly(dimethyl siloxane), poly(dipropyl siloxane), poly(tetramethylenephenylene diacetate), poly(tetramethylene trithiodicarboxylate),poly(trimethylene dodecane dioate), poly(m-xylene), poly(p-xylylenepimelamide), and combinations thereof. The semicrystalline resins mayhave any suitable weight average molecular weight Mw, such as from about7,000 to about 200,000, or from about 10,000 to about 150,000, or fromabout 15,000 to about 120,000; and any suitable number average molecularweight Mn, such as from about 1,000 to about 60,000, or from about 3,000to about 50,000, or from about 5,000 to about 40,000.

The crystalline resin may possess a melting point of, for example, fromabout 30° C. to about 120° C., such as from about 50° C. to about 90°C., or from about 60° C. to about 80° C. The crystalline resin may have,for example, a number average molecular weight (Mn), as measured by gelpermeation chromatography (GPC) of, for example, from about 1,000 toabout 50,000, such as from about 2,000 to about 25,000, or from about3,000 to about 20,000. The crystalline resin may have a weight averagemolecular weight (Mw) of the resin of, for example, from about 2,000 toabout 100,000, such as from about 3,000 to about 80,000, or from about4,000 to about 70,000, as determined by GPC using polystyrene standards.The molecular weight distribution (Mw/Mn) of the crystalline resin is,for example, from about 2 to about 6, such as from about 2 to about 4.

The crystalline resins may be prepared through polycondensation byreacting an organic diol and an organic diacid in the presence of apolycondensation catalyst. However, the crystalline polyester resin neednot be made by such a method. A stoichiometric equimolar ratio oforganic diol and organic diacid may be used, where the boiling point ofthe organic diol is from about 180° C. to about 230° C., an excessamount of diol may be utilized and removed during the polycondensationmethod. The amount of catalyst may vary, and may be selected in anamount, for example, of from about 0.01 to about 1 mole percent of theresin. Additionally, in place of an organic diacid, an organic diestercan also be selected. Examples of suitable organic diols and organicdiesters are described below.

Embodiments of the toner particle may include an amorphous polyester.Examples of amorphous polyesters suitable for use herein includeamorphous polyester resins, branched amorphous polyester resins, andlinear amorphous polyester resins.

Amorphous polyester resins may generally be prepared by thepolycondensation of a diol, and a diacid or a diester.

Examples of diols suitable for the preparation of amorphous polyestersmay include, but are not limited to, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol,2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol,dodecanediol, bis(hyroxyethyl)-bisphenol A,bis(2-hyroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethyleneglycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene, andmixtures thereof. The amount of organic diol may vary, and may be, forexample, from about 45 to about 52 mole percent of the resin. However,less diol may be used in some embodiments where the polyester-wax resinis to be used to form toner particles by an emulsion aggregation methodbecause, as described above, excess acid may be necessary.

Examples of diacids or diesters suitable for the preparation ofamorphous polyesters may include, but are not limited to, dicarboxylicacids or diesters selected from terephthalic acid, phthalic acid,isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconicacid, succinic acid, succinic anhydride, dodecylsuccinic acid,dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipicacid, pimelic acid, suberic acid, azelaic acid, dodecanediacid, dimethylterephthalate, diethyl terephthalate, dimethylisophthalate,diethylisophthalate, dimethylphthalate, phthalic anhydride,diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate,dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, andmixtures thereof. The diacid or diester constitute, for example, fromabout 45 to about 52 mole percent of the resin.

Branched amorphous polyester resins may be prepared by thepolycondensation of an organic diol, a diacid or diester, a multivalentpolyacid or polyol as the branching agent and a polycondensationcatalyst. Branching agents to generate branched amorphous polyesterresins include, for example, multivalent polyacids such as1,2,4-benzene-tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid,2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylicacid, 1,2,5-hexanetricarboxylic acid,1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane,tetra(methylene-carboxyl)methane, and 1,2,7,8-octanetetracarboxylicacid, acid anhydrides thereof, and lower alkyl esters thereof; amultivalent polyol such as sorbitol, 1,2,3,6-hexanetetrol,1,4-sorbitane, pentaerythritol, dipentaerythritol, tripentaerythritol,sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol,2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane,trimethylolpropane, 1,3,5-trihydroxymethylbenzene, mixtures thereof, andthe like. The branching agent may be selected in amounts from about 0.1to about 5 mole percent of the resin.

Embodiments of the amorphous resins may possess, for example, a numberaverage molecular weight (Mn), as measured by gel permeationchromatography (GPC), of from about 10,000 to about 500,000, such asfrom about 5,000 to about 250,000; or from about 7,000 to about 200,000.The amorphous resin may possess, for example, a weight average molecularweight (Mw) of, for example, from about 20,000 to about 600,000, and forexample from about 7,000 to about 300,000, or from about 8,000 to about200,000 as determined by GPC using polystyrene standards. The molecularweight distribution (Mw/Mn) of the amorphous resin may be, for example,from about 1.5 to about 6, such as from about 2 to about 5, or fromabout 2 to about 4.

Polyester-Wax Resin

As explained above, embodiments provide a unique method of chemicallyattaching a liquid bio-based oil to a polyester chain. The resultingpolyester-wax resin includes a bio-based oil that is chemicallyincorporated into the main chain of the polyester resin, such as apendent molecule. The method disclosed herein may include epoxidizing avinyl functional group in a polyester resin, synthesizing aminoderivatives of the bio-based oil, and covalently attaching the polyesterresin to the amino derivatives of the bio-based oil.

The polyester resin of the polyester-wax resin may be formed fromunsaturated monomers to provide the vinyl functional segment forepoxidation. Suitable unsaturated monomers may include, for example, aC₂ to C₂₀ unsaturated monomer, such as a C₃ to C₁₈ unsaturated monomer,or a C₄ to C₁₅ unsaturated monomer. The unsaturated monomers may includeunsaturated diols and diacids. Suitable monoethylenically unsaturateddi-acids are, for example, maleic acid, cyclohexene dicarboxylic acid,itaconic acid, mesaconic acid, fumaric acid, citraconic acid or theiranhydrides. Suitable monoethylenically unsaturated diols arecis-2-butene-1,4-diol, and 2-butyn-1,4-diol, 1,4-butenediol,1-propene-1,2-diol, 2-heptene-1,7-diol, 3-heptene-1,7-diol,2-hexene-1,6-diol, 3-hexene-1,6-diol, 1-pentene-1,5-diol or2-pentene-1,5-diol. A suitable unsaturated monoahydride may be maleicanhydride.

The epoxidation reaction may take place in any suitable solvent. Theepoxidation reaction may be performed at a temperature of from about −20to about 80° C. The reaction temperature may be, for example, about roomtemperature (about 20° C. to about 25° C.). The reaction time may be,for example, from about 5 minutes to about 72 hours, such as from about10 hours to about 14 hours, or about 12 hours.

Various epoxidizing reagents may be used for epoxidizing the unsaturatedunits in the polyester backbone. Suitable epoxidizing agents mayinclude, but are not limited to, epoxidizing agents containing aperoxide group, such as peracids, hydroperoxides, and other peroxides.The peracids may include, but are not limited to, for example,meta-chloroperoxybenzoic acid (MCPBA), peroxysulfuric acid, peroxyaceticacid, and peroxytrifluoroacetic acid. The hydroperoxides may include, byare not limited to, for example, hydrogen peroxide and tert-butylhydroperoxide. Other peroxides may include, but are not limited to, forexample, O₂ O₃, and magnesium monoperoxyphthalate hexahydrate (MMPP).

The reaction may yield from about 80% to over 90% polymer. Thenumber-average molecular weight (Mn) and polydispersity index (PDI) ofthe polyester resin may change only slightly, or may remain completelyunchanged, after the epoxidation. For example, little to no degradationof the polymer chain may be seen using this method. The polymer may becharacterized by ¹H NMR where the shift of the vinylic proton is easilyseen from 5.7 to 3.1 ppm.

The following is an example of the epoxidation reaction:

Binding a bio-based oil to a polyester resin may be achieved indifferent ways. In Shevachman, M., et al. “Chemical Binding of JojobaLiquid Wax to Polyethylene.” J. Am. Oil Chem. SOC. 2001, 78, 223-228,jojoba wax is bonded to polyethylene (PE) by two different methods. Thefirst method involves binding allylic bromo derivatives of jojoba(J-xBr) to aminated PE (PE-SO₂NH₂). The second method involves bindingallylic amino derivatives of jojoba (J-xNH₂) to chlorosulfonated PE(PE-SO₂Cl).

Allylic amino derivatives of the bio-based oil may be synthesized, forexample, through the allylic bromo derivative (J-xBr) route disclosed inShani, A., “Functionalization at the Double Bond Region of JojobaOil: 1. Bromine Derivatives.” J. Am. Oil Chem. SOC. 1981, 845-850. Anyhalogen atom may be used to synthesize allylic amino derivatives of thebio-based oil. The method may begin with a substitution reaction of ahalogen, such as bromine, to double bonds in the bio-based oil, followedby displacement of the halogen atoms by an azide ion. As disclosed inAvidon, V., et al., “Functionalization at the Double Bond Region ofJojoba Oil. 6. Production of Amines via Azides.” J. Am. Oil Chem. SOC.1994, 71, 993-997 (“Avidon”), another reaction may be the hydrogenationof the azides to diamine of the bio-based oil, as seen in an exemplaryscheme below using jojoba oil as the bio-based oil.

In embodiments, the covalent attachment or binding of the polyesterresin to the bio-based oil may occur through the reaction of the epoxidefunctional group on the unsaturated monomer within the polymer chain andthe amine functionality of the bio-based oil. In embodiments, both anamorphous polyester resin, such as poly(propoxylated bisphenol-Aco-fumarate) obtained from Reichold Chemicals, and a crystallinepolyester may contain the required unsaturated monomer units for theepoxidation reaction.

The epoxidation reaction may take place before or within the phaseinversion (PI) solvent system before emulsification is done, asdescribed below. The bio-based oil may be chemically bound to thepolyester after the solvent is removed via PT emulsification. Inembodiments, the latex emulsion may be used in the EA toner methodwithout the addition of a separate wax emulsion.

The following is an exemplary scheme for chemically bonding thebio-based oil to the polyester resin:

Crosslinking may occur if one of the NH₂ groups reacts with otherfunctional groups on adjacent polymers.

The onset glass transition temperature (Tg) of the polyester-wax resin,and the resulting toner, may be from about 50° C. to about 70° C., suchas from about 53° C. to about 67° C., or from about 56° C. to about 60°C. The softening temperature (Ts) of the polyester-wax resin, and theresulting toner, that is, the temperature at which the polyester-waxresin, and the resulting toner softens, may be from about 90° C. toabout 135° C., such as from about 95° C. to about 130° C. or from about105° C. to about 125° C.

Toner

The toner particle having the polyester-wax resin as described hereinand may be made by any suitable method. Although embodiments relating totoner particle production are described below with respect toemulsion-aggregation processes, any suitable method of preparing tonerparticles may be used, including chemical processes, such as suspensionand encapsulation processes disclosed in U.S. Pat. Nos. 5,290,654 and5,302,486, the disclosures of each of which are hereby incorporated byreference in their entirety.

The toner particle, in embodiments, may also be prepared using methodssuch as conventional jetted toner particles. Conventional jetted tonersare illustrated in a number of patents, such as U.S. Pat. Nos.6,177,221, 6,319,647, 6,365,316, 6,416,916, 5,510,220, 5,227,460,4,558,108, and 3,590,000, each of which is incorporated herein byreference in its entirety. Conventional jetted toners may comprisematerials described in the aforementioned references. As thesereferences fully describe conventional jetted toners made by processesother than the EA process and methods of making the same, furtherdiscussion on these points is omitted herein.

Emulsion Aggregation

As discussed above, the toner particles having the polyester-wax resinas described herein may be made by the emulsion aggregation method.

An example of a method for generating a resin emulsion for theproduction of toner particles having the polyester-wax resin isdisclosed in U.S. Pat. No. 7,029,817, which is incorporated herein inits entirety by reference. Emulsion aggregation toner dispersions may begenerated by other methods including, but not limited to, the meltmixing method disclosed in U.S. patent application Ser. No. 11/094,413,which is incorporated herein in its entirety by reference, and the phaseinversion method.

The polyester toner particles may be created by the emulsion aggregation(EA) method, which are illustrated in a number of patents, such as U.S.Pat. No. 5,593,807, U.S. Pat. No. 5,290,654, U.S. Pat. No. 5,308,734,and U.S. Pat. No. 5,370,963, each of which are incorporated herein byreference in their entireties. The polyester resin of the polyester-waxresin may comprise any of the polyester materials described in theaforementioned references.

In embodiments, toner compositions may be prepared by any knownemulsion-aggregation method. As described below, a method may includeaggregating a mixture of additives and the emulsion comprising apolyester-wax resin as disclosed herein, and then coalescing theaggregated mixture.

Polyester-Wax Resin Emulsion

The polyester-wax resin emulsion may be prepared by dissolving the resinin a suitable solvent. In embodiments, the resin emulsion may beprepared by dissolving a polyester-wax resin in a solvent. Crystallinepolyester emulsions may be similarly prepared.

Suitable solvents include alcohols, ketones, esters, ethers, chlorinatedsolvents, nitrogen containing solvents and mixtures thereof. Specificexamples of suitable solvents include acetone, methyl acetate, methylethyl ketone, tetrahydrofuran, cyclohexanone, ethyl acetate, N,Ndimethylformamide, dioctyl phthalate, toluene, xylene, benzene,dimethylsulfoxide, mixtures thereof, and the like. The resin may bedissolved in the solvent at elevated temperature of from about 40° C. toabout 80° C., such as from about 50° C. to about 70° C. or from about60° C. to about 65° C. The dissolution temperature may be lower than theglass transition temperature of the wax and resin. In embodiments, theresin is dissolved in the solvent at an elevated temperature, but belowthe boiling point of the solvent, such as from about 2° C. to about 15°C. below the boiling point of the solvent, such as from about 3° C. toabout 13° C. below the boiling point of the solvent, or from about 5° C.to about 10° C. below the boiling point of the solvent.

The resin may be dissolved in the solvent, and mixed into an emulsionmedium, for example water, such as deionized water optionally containinga stabilizer and a surfactant. Examples of suitable stabilizers includewater-soluble alkali metal hydroxides, such as sodium hydroxide,potassium hydroxide, lithium hydroxide, beryllium hydroxide, magnesiumhydroxide, calcium hydroxide, or barium hydroxide; ammonium hydroxide;alkali metal carbonates, such as sodium bicarbonate, lithiumbicarbonate, potassium bicarbonate, lithium carbonate, potassiumcarbonate, sodium carbonate, beryllium carbonate, magnesium carbonate,calcium carbonate, barium carbonate or cesium carbonate; or mixturesthereof. In embodiments, the stabilizer is sodium bicarbonate orammonium hydroxide. When the stabilizer is used in the composition, itis typically present in amounts of from about 0.1 percent to about 5percent, such as from about 0.5 percent to about 3 percent, by weight ofthe resin. When such salts are added to the composition as a stabilizer,in embodiments, incompatible metal salts are not present in thecomposition. For example, when these salts are used, the compositionshould be completely or essentially free of zinc and other incompatiblemetal ions, for example, Ca, Fe, Ba, etc., that form water-insolublesalts. The term “essentially free” refers, for example, to theincompatible metal ions present at a level of less than about 0.01percent, such as less than about 0.005 percent or less than about 0.001percent, by weight of the wax and resin. The stabilizer may be added tothe mixture at ambient temperature, or it may be heated to the mixturetemperature prior to addition.

Optionally, an additional stabilizer, such as a surfactant, may be addedto the aqueous emulsion medium to afford additional stabilization to theresin. Suitable surfactants include anionic, cationic and nonionicsurfactants. In embodiments, the use of anionic and nonionic surfactantsmay help stabilize the aggregation method in the presence of thecoagulant, which otherwise could lead to aggregation instability.

Anionic surfactants include sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl, sulfates and sulfonates, abitic acid, and the NEOGEN brandof anionic surfactants. An example of a suitable anionic surfactant isNEOGEN R-K available from Daiichi Kogyo Seiyaku Co. Ltd. (Japan), orTAYCAPOWER BN2060 from Tayca Corporation (Japan), which consistsprimarily of branched sodium dodecyl benzene sulfonate.

Examples of cationic surfactants include dialkyl benzene alkyl ammoniumchloride, lauryl trimethyl ammonium chloride, alkylbenzyl methylammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkoniumchloride, cetyl pyridinium bromide, C₁₂, C₁₅, C₁₇ trimethyl ammoniumbromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL and ALKAQUAT available fromAlkaril Chemical Company, SANISOL (benzalkonium chloride), availablefrom Kao Chemicals, and the like. An example of a suitable cationicsurfactant is SANISOL B-50 available from Kao Corporation, whichconsists primarily of benzyl dimethyl alkonium chloride.

Examples of nonionic surfactants include polyvinyl alcohol, polyacrylicacid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose,hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetylether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether,polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether,polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether,polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy)ethanol, available from Rhone-Poulenc Inc. as IGEPAL CA-210, IGEPALCA-520, IGEPAL CA-720, IGEPAL CO-890, IGEPAL CO-720, IGEPAL CO-290,IGEPAL CA-210, ANTAROX 890 and ANTAROX 897. An example of a suitablenonionic surfactant is ANTAROX 897 available from Rhone-Poulenc Inc.,which consists primarily of alkyl phenol ethoxylate.

After the stabilizer or stabilizers are added, the resultant mixture maybe mixed or homogenized for any amount of time.

Next, the mixture is heated to flash off the solvent, and then cooled toroom temperature (about 20° C. to about 25° C.). For example, thesolvent flashing may be conducted at any suitable temperature above theboiling point of the solvent that will flash off the solvent, such as atemperature of from about 60° C. to about 100° C., such as from about70° C. to about 90° C. or about 80° C., although the temperature may beadjusted based on, for example, the particular wax, resin, and solventused.

Following the solvent flash step, the polyester-wax resin emulsion, mayhave an average particle diameter in the range of from about 100 toabout 500 nanometers, such as from about 130 to about 300 nanometers asmeasured with a Honeywell MICROTRAC® UPA150 particle size analyzer.

In alternative embodiments, the polyester-wax resin emulsion may beprepared by a suitable method, such as, solvent flash or phase inversionemulsification and the like.

A pre-toner mixture is prepared by combining the colorant, andoptionally other materials, such as a surfactant, and the polyester-waxresin emulsion. In embodiments, the pH of the pre-toner mixture isadjusted to from about 2.5 to about 4. The pH of the pre-toner mixturemay be adjusted by an acid such as, for example, acetic acid, nitricacid or the like. Additionally, in embodiments, the pre-toner mixtureoptionally may be homogenized. If the pre-toner mixture is homogenized,homogenization may be accomplished by mixing at from about 600 to about4,000 revolutions per minute. Homogenization may be accomplished by anysuitable means, including, for example, an IKA ULTRA TURRAX T50 probehomogenizer.

Aggregation

Any suitable aggregating agent may be utilized to form a toner particleusing the above pre-toner mixture. Suitable aggregating agents include,for example, aqueous solutions of a divalent cation or a multivalentcation material. The aggregating agent may be, for example, polyaluminumhalides such as polyaluminum chloride (PAC), or the correspondingbromide, fluoride, or iodide, polyaluminum silicates such aspolyaluminum sulfosilicate (PASS), and water soluble metal saltsincluding aluminum chloride, aluminum nitrite, aluminum sulfate,potassium aluminum sulfate, calcium acetate, calcium chloride, calciumnitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesiumnitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate,zinc chloride, zinc bromide, magnesium bromide, copper chloride, coppersulfate, and combinations thereof. In embodiments, the aggregating agentmay be added to the mixture at a temperature that is below the glasstransition temperature (Tg) of the resin.

In embodiments, the aggregating agent may be added to the mixtureutilized to form a toner in an amount of, for example, from about 0.01%to about 8% by weight, in embodiments from about 0.1% to about 1% byweight, in other embodiments from about 0.15% to about 0.8% by weight,of the resin in the mixture, although amounts outside these ranges maybe utilized. This may provide a sufficient amount of agent foraggregation.

To control aggregation and subsequent coalescence of the particles, inembodiments the aggregating agent may be metered into the mixture overtime. For example, the agent may be metered into the mixture over aperiod of from about 5 to about 240 minutes, in embodiments from about30 to about 200 minutes, although more or less time may be used. Theaddition of the agent may occur while the mixture is maintained understirred conditions, in embodiments from about 50 rpm to about 1,000 rpm,in other embodiments from about 100 rpm to about 500 rpm, althoughspeeds outside these ranges may be utilized. The addition of the agentmay also occur while the mixture is maintained at a temperature that isbelow the glass transition temperature of the resin discussed above, inembodiments from about 30° C. to about 90° C., in embodiments from about35° C. to about 70° C., although temperatures outside these ranges maybe utilized.

The particles may be permitted to aggregate until a predeterminedparticle size is obtained. A predetermined size refers to the particlesize to be obtained as determined prior to formation, and the particlesize being monitored during the growth process until such particle sizeis reached. Samples may be taken during the growth process and analyzed,for example with a Coulter Counter, for average particle size. Theaggregation thus may proceed by maintaining the elevated temperature, orslowly raising the temperature to, for example, from about 30° C. toabout 99° C., and holding the mixture at this temperature for a timefrom about 0.5 hours to about 10 hours, in embodiments from about hour 1to about 5 hours (although times outside these ranges may be utilized),while maintaining stirring, to provide the aggregated particles. Oncethe predetermined particle size is reached, the growth process ishalted. In embodiments, the predetermined particle size may be the sizeof the final toner particles.

The growth and shaping of the particles following addition of theaggregation agent may be accomplished under any suitable conditions. Forexample, the growth and shaping may be conducted under conditions inwhich aggregation occurs separate from coalescence. For separateaggregation and coalescence stages, the aggregation process may beconducted under shearing conditions at an elevated temperature, forexample of from about 40° C. to about 90° C., in embodiments from about45° C. to about 80° C. (although temperatures outside these ranges maybe utilized), which may be below the glass transition temperature of theresin as discussed above.

Once the final size of the toner particles is achieved, the pH of themixture may be adjusted with a base to a value of from about 3 to about10, and in embodiments from about 5 to about 9, although a pH outsidethese ranges may be utilized. The adjustment of the pH may be utilizedto freeze, that is to stop, toner growth. The base utilized to stoptoner growth may include any suitable base such as, for example, alkalimetal hydroxides such as, for example, sodium hydroxide, potassiumhydroxide, ammonium hydroxide, combinations thereof, and the like. Inembodiments, ethylene diamine tetraacetic acid (EDTA) may be added tohelp adjust the pH to the values noted above.

Core-Shell Structure

The toner particles derived from the polyester-wax resin describedherein may have a core-shell structure. The toner core may comprise ahigh molecular weight amorphous resin, a low molecular weight amorphousresin, and a crystalline polyester resin with a bio-based oil, such as,for example, jojoba oil chemically bonded to its backbone. The shell maycomprise a high molecular weight amorphous resin and a lower molecularweight amorphous resin. The shell may only comprise amorphous resin.

In embodiments, after aggregation, but prior to coalescence, a resincoating may be applied to the aggregated particles to form a shellthereover. Any resin described above as suitable for forming the tonerresin may be utilized as the shell.

In embodiments, resins which may be utilized to form a shell include,but are not limited to, crystalline polyesters described above, and/orthe amorphous resins described above for use as the core. For example,in embodiments, a polyalkoxylated bisphenol A-co-terephthalicacid/dodecenylsuccinic acid/trimellitic acid resin, a polyalkoxylatedbisphenol A-co-terephthalic acid/fumaric acid/dodecenylsuccinic acidresin, or a combination thereof, may be combined with apolydodecanedioic acid-co-1,9-nonanediol crystalline polyester resin toform a shell. Multiple resins may be utilized in any suitable amounts.

The shell resin may be applied to the aggregated particles by any methodwithin the purview of those skilled in the art. In embodiments, theresins utilized to form the shell may be in an emulsion including anysurfactant described above. The emulsion possessing the resins may becombined with the aggregated particles described above so that the shellforms over the aggregated particles. In embodiments, the shell may havea thickness of up to about 5 microns, in embodiments of from about 0.1to about 2 microns, in other embodiments, from about 0.3 to about 0.8microns, over the formed aggregates, although thicknesses outside ofthese ranges may be obtained.

The formation of the shell over the aggregated particles may occur whileheating to a temperature of from about 30° C. to about 80° C. inembodiments from about 35° C. to about 70° C., although temperaturesoutside of these ranges may be utilized. The formation of the shell maytake place for a period of time of from about 5 minutes to about 10hours, in embodiments from about 10 minutes to about 5 hours, althoughtimes outside these ranges may be used.

For example, in some embodiments, the toner process may include forminga toner particle by mixing the polymer latexes, in the presence of a waxdispersion and the surface-treated pigment of this disclosure,including, for example, the surface-treated titanium dioxide describedabove, with an optional coagulant while blending at high speeds. Theresulting mixture having a pH of, for example, of from about 2 to about3, is aggregated by heating to a temperature below the polymer resin Tgto provide toner size aggregates. Optionally, additional latex can beadded to the formed aggregates providing a shell over the formedaggregates. The pH of the mixture may then be changed, for example bythe addition of a sodium hydroxide solution, until a pH of about 7 maybe achieved.

Coalescence

Following aggregation to a particle size and application of any optionalshell, the particles may then be coalesced to the final shape, thecoalescence being achieved by, for example, heating the mixture to atemperature of from about 45° C. to about 100° C., in embodiments fromabout 55° C. to about 99° C. (although temperatures outside of theseranges may be used), which may be at or above the glass transitiontemperature of the resins utilized to form the toner particles, and/orreducing the stirring, for example to from about 100 rpm to about 1,000rpm, in embodiments from about 200 rpm to about 800 rpm (although speedsoutside of these ranges may be used). The fused particles can bemeasured for shape factor or circularity, such as with a Sysmex FPIA2100 analyzer, until a shape is achieved.

Higher or lower temperatures may be used, it being understood that thetemperature is a function of the resins used for the binder. Coalescencemay be accomplished over a period of from about 0.01 hours to about 9hours, in embodiments from about 0.1 hours to about 4 hours (althoughtimes outside of these ranges may be used).

After aggregation and/or coalescence, the mixture may be cooled to roomtemperature, such as from about 20° C. to about 25° C. The cooling maybe rapid or slow. A suitable cooling method may include introducing coldwater to a jacket around the reactor. After cooling, the toner particlesmay be optionally washed with water, and then dried. Drying may beaccomplished by any suitable method for drying including, for example,freeze-drying.

Other Components and Additives

In embodiments, the method may include the use of surfactants,emulsifiers, and other additives, such as those discussed above.Likewise, various modifications of the above method will be apparent andare encompassed herein.

The toner particles described herein may further include othercomponents, such as colorants, and various external additives. Colorantincludes pigments, dyes, mixtures of dyes, mixtures of pigments,mixtures of dyes and pigments, and the like.

When present, the colorant may be added in an effective amount of, forexample, from about 1 to about 25 percent by weight of the particle,such as from about 2 to about 12 weight percent. Suitable examplecolorants include, for example, carbon black like REGAL 330® magnetites,such as Mobay magnetites MO8029™, MO8060™; Columbian magnetites; MAPICOBLACKS™ and surface treated magnetites; Pfizer magnetites CB4799™,CB5300™, CB5600™, MCX6369™; Bayer magnetites, BAYFERROX8600™, 8610™;Northern Pigments magnetites, NP-604™, NP-608™; Magnox magnetitesTMB-100™, or TMB-104™; and the like. As colored pigments, there may beselected cyan, magenta, yellow, red, green, brown, blue or mixturesthereof. Specific examples of pigments include phthalocyanine HELIOGENBLUE L6900™, D6840™, D7080™, D7020™, PYLAM OIL BLUE™, PYLAM OIL YELLOW™,PIGMENT BLUE 1™ available from Paul Uhlich & Company, Inc., PIGMENTVIOLET 1™, PIGMENT RED 48™, LEMON CHROME YELLOW DCC 1026™, E.D.TOLUIDINE RED™ and BON RED C™ available from Dominion Color Corporation,Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL™, HOSTAPERM PINK E™ fromHoechst, and CINQUASIA MAGENTA™ available from E.I. DuPont de Nemours &Company, and the like. Generally, colorants that may be selected areblack, cyan, magenta, or yellow, and mixtures thereof. Examples ofmagentas are 2,9-dimethyl-substituted quinacridone and anthraquinone dyeidentified in the Color Index as CI 60710, CI Dispersed Red 15, diazodye identified in the Color Index as CI 26050, CI Solvent Red 19, andthe like. Illustrative examples of cyans include copper tetra(octadecylsulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed inthe Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue,identified in the Color Index as CI 69810, Special Blue X-2137, and thelike; while illustrative examples of yellows are diarylide yellow3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified inthe Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl aminesulfonamide identified in the Color Index as Foron Yellow SE/GLN, CIDispersed Yellow 33 2,5-dimethoxy-4-sulfonanilidephenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide, and Permanent YellowFGL. Colored magnetites, such as mixtures of MAPICO BLACK™, and cyancomponents may also be selected as colorants. Other known colorants maybe selected, such as Levanyl Black A-SF (Miles, Bayer) and SunsperseCarbon Black LHD 9303 (Sun Chemicals), and colored dyes such as NeopenBlue (BASF), Sudan Blue OS (BASF), PV Fast Blue B2G01 (AmericanHoechst), Sunsperse Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA(Ciba-Geigy), Paliogen Blue 6470 (BASF), Sudan III (Matheson, Coleman,Bell), Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman,Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF), PaliogenOrange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen Yellow152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840(BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (Hoechst), PermanentYellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), SunsperseYellow YHD 6001 (Sun Chemicals), Suco-Gelb L1250 (BASF), Suco-YellowD1355 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830(BASF), Cinquasia Magenta (DuPont), Lithol Scarlet D3700 (BASF),Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (UgineKuhlmann of Canada), E.D. Toluidine Red (Aldrich), Lithol Rubine Toner(Paul Uhlich), Lithol Scarlet 4440 (BASF), Bon Red C (Dominion ColorCompany), Royal Brilliant Red RD-8192 (Paul Uhlich), Oracet Pink RF(Ciba-Geigy), Paliogen Red 3871K (BASF), Paliogen Red 3340 (BASF), andLithol Fast Scarlet L4300 (BASF).

In embodiments, the toner particles may be curable upon exposure to UVradiation, for example, where the polyester resin of the polyester-waxresin includes unsaturated moieties as described above. In suchembodiments, the toner may further include suitable photoinitiators,such as UV-photoinitiators including, but not limited to,hydroxycyclohexylphenyl ketones; other ketones such as alpha-aminoketone and 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone;benzoins; benzoin alkyl ethers; benzophenones, such as2,4,6-trimethylbenzophenone and 4-methylbenzophenone;trimethylbenzoylphenylphosphine oxides such as2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide orphenylbis(2,4,6-trimethylvbenzyoyl) phosphine oxide (BAPO) available asIRGACURE 819 from Ciba; azo compounds; anthraquinones and substitutedanthraquinones, such as, for example, alkyl substituted or halosubstituted anthraquinones; other substituted or unsubstitutedpolynuclear quinines; acetophenones, thioxanthones; ketals;acylphosphines; and mixtures thereof. Other examples of photoinitiatorsinclude, but not limited to, 2-hydroxy-2-methyl-1-phenyl-propan-1-oneand 2-isopropyl-9H-thioxanthen-9-one. In embodiments, the photoinitiatoris one of the following compounds or a mixture thereof: ahydroxycyclohexylphenyl ketone, such as, for example,2-hydroxy-4′-hydroxyethoxy-2-methylpropiophenone or1-hydroxycyclohexylphenyl ketone, such as, for example, IRGACURE® 184(Ciba-Geigy Corp., Tarrytown, N.Y.), having the structure:

a trimethylbenzoylphenylphosphine oxide, such as, for example,ethyl-2,4,6-trimethylbenzoylphenylphosphinate, such as, for example,LUCIRIN® TPO-L (BASF Corp.), having the formula

a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone, suchas, for example, SARCURE™ SR1137 (Sartomer); a mixture of2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and2-hydroxy-2-methyl-1-phenyl-propan-1-one, such as, for example, DAROCUR®4265 (Ciba Specialty Chemicals); alpha-amino ketone, such as, forexample, IRGACURE® 379 (Ciba Specialty Chemicals);4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, such as, forexample, IRGACURE® 2959 (Ciba Specialty Chemicals);2-isopropyl-9H-thioxanthen-9-one, such as, for example, DAROCUR® ITX(Ciba Specialty Chemicals); and mixtures thereof.

The toner composition may contain from about 0.5 to about 15 wt %photoinitiator, such as from about 1 to about 15 wt %, or from about 3to about 12 wt %. The photoinitiator may be a UV-photoinitiator. Ofcourse, other amounts may be used.

The toner may also include any suitable surface additives. Examples ofsurface additives are surface treated fumed silicas, for example TS-530from Cabosil Corporation, with an 8 nanometer particle size and asurface treatment of hexamethyldisilazane; NAX50 silica, obtained fromDeGussa/Nippon Aerosil Corporation, coated with HMDS; DTMS silica,obtained from Cabot Corporation, comprised of a fumed silica silicondioxide core L90 coated with DTMS; H2050EP, obtained from Wacker Chemie,coated with an amino functionalized organopolysiloxane; metal oxidessuch as TiO₂, for example MT-3103 from Tayca Corp. with a 16 nanometerparticle size and a surface treatment of decylsilane; SMT5103, obtainedfrom Tayca Corporation, comprised of a crystalline titanium dioxide coreMT500B coated with DTMS (decyltrimethoxysilane); P-25 from DegussaChemicals with no surface treatment; alternate metal oxides such asaluminum oxide, and as a lubricating agent, for example, stearates orlong chain alcohols, such as UNILIN 700™, and the like. In general,silica is applied to the toner surface for toner flow, triboenhancement, admix control, improved development and transfer stability,and higher toner blocking temperature. TiO₂ is applied for improvedrelative humidity (RH) stability, tribo control and improved developmentand transfer stability. Examples of suitable SiO₂ and TiO₂ are thosesurface treated with compounds including DTMS (decyltrimethoxysilane) orHMDS (hexamethyldisilazane).

The SiO₂ and TiO₂ may generally possess a primary particle size greaterthan approximately 30 nanometers, or at least 40 nanometers, with theprimary particles size measured by, for instance, transmission electronmicroscopy (TEM) or calculated (assuming spherical particles) from ameasurement of the gas absorption, or BET, surface area. TiO₂ is foundto be especially helpful in maintaining development and transfer over abroad range of area coverage and job run length. The SiO₂ and TiO₂ aremore specifically applied to the toner surface with the total coverageof the toner ranging from, for example, about 140 to about 200 percenttheoretical surface area coverage (SAC), where the theoretical SAC(hereafter referred to as SAC) is calculated assuming all tonerparticles are spherical and have a diameter equal to the volume mediandiameter of the toner as measured in the standard Coulter Countermethod, and that the additive particles are distributed as primaryparticles on the toner surface in a hexagonal closed packed structure.Another metric relating to the amount and size of the additives is thesum of the “SAC×Size” (surface area coverage times the primary particlesize of the additive in nanometers) for each of the silica and titaniaparticles, or the like, for which all of the additives should, morespecifically, have a total SAC×Size range of, for example, about 4,500to about 7,200. The ratio of the silica to titania particles isgenerally from about 50 percent silica/50 percent titania to about 85percent silica/15 percent titania (on a weight percentage basis).

Calcium stearate and zinc stearate may be selected as an additive forembodiments of the toner. The calcium and zinc stearate primarilyprovide lubricating properties. Also, the calcium and zinc stearate canprovide developer conductivity and tribo enhancement, both due to itslubricating nature. In addition, calcium and zinc stearate enableshigher toner charge and charge stability by increasing the number ofcontacts between toner and carrier particles. A suitable example is acommercially available calcium and zinc stearate with greater than about85 percent purity, for example from about 85 to about 100 percent pure,for the 85 percent (less than 12 percent calcium oxide and free fattyacid by weight, and less than 3 percent moisture content by weight) andwhich has an average particle diameter of about 7 microns and isavailable from Ferro Corporation (Cleveland, Ohio). Examples are SYNPRO®Calcium Stearate 392A and SYNPRO® Calcium Stearate NF Vegetable or ZincStearate-L. Another example is a commercially available calcium stearatewith greater than 95 percent purity (less than 0.5 percent calcium oxideand free fatty acid by weight, and less than 4.5 percent moisturecontent by weight), and which stearate has an average particle diameterof about 2 microns and is available from NOF Corporation (Tokyo, Japan).In embodiments, the toners contain from, for example, about 0.1 to about5 weight percent titania, about 0.1 to about 8 weight percent silica, orfrom about 0.1 to about 4 weight percent calcium or zinc stearate.

Toner Properties

In embodiments, the charge distribution for the toner particles in boththe A-zone and the C-zone may be from about −2 mm to about −25 mmdisplacement, such as from about −4 mm to about −20 mm displacement.

The charge performance or distribution of a toner is frequentlydemarcated as q/d (mm). The toner charge (q/d) is measured as themidpoint of the toner charge distribution. The charge is reported inmillimeters of displacement from the zero line in a charge spectrographusing an applied transverse electric field of 100 volts per cm. The q/dmeasure in mm may be converted to a value in fC/μm by multiplying thevalue in mm by 0.092.

In embodiments, the ratio of the charge distribution in the A-zone tothe C-zone may be as close to 1 as possible. This ratio (C-zone/A-zone)is frequently referred to as the relative humidity (RH) sensitivity bythose skilled in the art. In embodiments, the RH sensitivity may be in arange of less than about 10, such as from about 0.03 to about 8.

The toner particles described herein also exhibit acceptable tonercohesion. Toner cohesion may be measured using a Hosokawa Micron PT-Rtester, available from Micron Powders Systems. Toner cohesion istypically expressed in percent (%) cohesion. Percent cohesion may bemeasured by placing a known mass of toner, for example 2 grams, on topof a set of stacked screens, for example a top screen that has 53 micronmesh or openings, a middle screen that has 45 micron mesh or openings,and a bottom screen that has 38 micron mesh or openings, and vibratingthe screens and toner for a fixed time at a fixed vibration amplitude,for example for 90 seconds at 1 millimeter vibration amplitude. Allscreens are made of stainless steel. The percent cohesion is thencalculated as follows:% cohesion=50·A+30·B+10·Cwhere A is the mass of toner remaining on the 53 micron screen, B is themass of toner remaining on the 45 micron screen, and C is the mass oftoner remaining on the 38 micron screen. The percent cohesion of thetoner is related to the amount of toner remaining on each of the screensat the end of the time. A percent cohesion value of 100% corresponds toall the toner remaining on the top screen at the end of the vibrationstep and a percent cohesion of 0% corresponds to all of the tonerpassing through all three screens, in other words, no toner remaining onany of the three screens at the end of the vibration step. The greaterthe percent cohesion for toners, the less the toner particles are ableto flow. In embodiments, the toners may have a percent cohesion in therange of, for example, from about 30% to about 80%, such as from about35% to about 75%, or from about 40% to about 65%.Developer

The toner particles of all embodiments may be included in developercompositions. In embodiments, developer compositions comprise singlecomponent developers of toner only, and two component developers oftoner particles mixed with carrier particles. In some embodiments, thetoner concentration in the developer composition may range from about 1weight percent to about 25 weight percent, such as from about 2 weightpercent to about 15 weight percent, of the total weight of the developercomposition.

Examples of carrier particles suitable for mixing with the toner includethose particles that are capable of triboelectrically obtaining a chargeof opposite polarity to that of the toner particles, such as granularzircon, granular silicon, glass, steel, nickel, ferrites, iron ferrites,silicon dioxide, and the like.

The selected carrier particles may be used with or without a coating,the coating generally being comprised of fluoropolymers, such aspolyvinylidene fluoride resins; terpolymers of styrene; methylmethacrylate; silanes, such as triethoxy silane; tetrafluoroethylenes;other known coatings; and the like.

Imaging

In embodiments, any known type of image development system may be usedin an image developing device, including, for example, magnetic brushdevelopment, jumping single-component development, hybrid scavengelessdevelopment (HSD), etc. These development systems are known in the art,and further explanation of the operation of these devices to form animage is thus not necessary herein. Once the image is formed withtoners/developers described herein via a suitable image developmentmethod such as any one of the aforementioned methods, the image is thentransferred to an image receiving medium such as paper and the like. Inan embodiment described herein, the toners may be used in developing animage in an image-developing device utilizing a fixing member, such as afuser roll member. The fixing member suitable for use with the tonerhaving a polyester-wax resin as described herein may be an oil-lessfixing member or a low oil fixing member. As used herein and “oil-lessfixing member” refers to a fixing member that is utilized with no oil.As used herein a “low oil fixing member” refers to a fixing member, orfuser, that use from about 0.5 μL of oil per print/copy to about 1 μL ofoil per print/copy. In contrast, fixing members that are not oil-lessand not low oil fixing members are usual used with from about 5 μL ofoil per print/copy to about 10 μL of oil per print/copy.

A toner having the polyester-wax resin described herein is particularlysuitable for use with an oil-less fixing member or a low oil fixingmember because the wax is present in the toner without any preparationdisadvantages as described herein. Fuser roll members are contact fusingdevices that are known in the art, in which heat and pressure from theroll are used in order to fuse the toner to the image-receiving medium.Typically, the fuser member may be heated to a temperature just abovethe fusing temperature of the toner, that is, to temperatures of fromabout 80° C. to about 150° C. or more.

Embodiments described above will now be further illustrated by way ofthe following examples, which are not intended to limit the disclosure.

EXAMPLES Preparation of Crystalline Resin Emulsion Including aCrystalline Polyester Resin,Copoly(Ethylene-Dodecanoate)-Copoly-(Ethylene-Fumarate), Derived fromDodecanedioic Acid, Ethylene Glycol and Fumaric Acid

A one liter Parr reactor equipped with a heating mantle, mechanicalstirrer, bottom drain valve and distillation apparatus was charged withdodecanedioic acid (about 443.6 grams), fumaric acid (about 18.6 grams),hydroquinone (about 0.2 grams), n-butylstannoic acid (FASCAT 4100)catalyst (about 0.7 grams), and ethylene glycol (about 248 grams). Thematerials were stirred and slowly heated to about 150° C. over about 1hour under a stream of CO₂. The temperature was then increased by about15° C., and subsequently about 10° C. intervals, every 30 minutes, toabout 180° C.

During this time, water was distilled as a byproduct. The temperaturewas then increased by about 5° C. intervals over about a 1 hour periodto about 195° C. The pressure was then reduced to about 0.03 mbar overabout a 2 hour period and any excess glycols were collected in thedistillation receiver. The resin was returned to atmospheric pressureunder a stream of CO₂ and then trimellitic anhydride (about 12.3 grams)was added. The pressure was slowly reduced to about 0.03 mbar over about10 minutes and held there for about another 40 minutes. The crystallineresin, copoly(ethylene-dodecanoate)-copoly-(ethylene-fumarate, wasreturned to atmospheric pressure and then drained through the bottomdrain valve to give a resin with a viscosity of about 87 Pas (measuredat about 85° C.), an onset melting of about 69° C., a melt pointtemperature peak of about 78° C., and a recrystallization peak oncooling of about 56° C., as measured by the Dupont Differential Scanningcalorimeter. The acid value of the resin was found to be about 12meq/KOH.

Epoxidation of the Vinyl Functional Group in the Polyester ResinBackbone

About 150 grams ofcopoly(Ethylene-Dodecanoate)-Copoly-(Ethylene-Fumarate) was dissolved inabout 2.5 liters of dichloromethane to which about 205 grams of coldmeta-chloroperbenzoic acid (mCPBA, 77% grade, obtained fromSigma-Aldrich) was added. The reaction mixture was stirred overnight,for a period of time from about 12 hours to about 24 hours, at roomtemperature (about 20° C. to about 25° C.), and then filtered to removeany insoluble material. The filtrate was concentrated under reducedpressure of about 50 torr and then added to slowly stirring methanol atabout 300 revolutions per minute (rpm) to induce precipitation. Theresulting white, fibrous material was collected by filtration and dried.¹H NMR spectroscopy showed the absence of a 5.3 ppm signal correspondingto alkene protons and the presence of a new signal at 2.4 ppm,corresponding to epoxide ring protons

Functionalization of Jojoba Oil with Bromine

To a solution of 236 g of jojoba oil (0.4 mol) in 1 liter of CCl₂, asolution of 128 g Br₂ (0.8 mol) in 200 ml CCl₂ was added dropwise over aperiod of 6 hours. The reaction mixture was kept at 17-20° C. by a coldwater bath during this time. The reaction mixture was almost colourlessduring the addition. Any unreacted bromine was washed away with Na₂SO₃solution during work up.

Synthesis of Vinylic Jojoba Diazide

A solution of 233.2 g (0.256 mol) of brominated jojoba oil in 1 liter ofDMF with 72 g (1.12 mol) of activated NaN₃ (sodium azide) was stirredfor 6 hours at 90-94° C. in an oil bath. The crude product yield was174.8 g after standard workup. After purification, the yield of thefinal light yellow oil was 140.0 g.

Synthesis of Diaminojojoba from Vinylic Jojoba Diazide

A mixture of 138.6 g (0.167 mol) of diazided jojoba oil in 2.4 litersethanol with 15.75 g of 10% Pd/C (palladium on carbon, 10 wt. % loading,matrix activated carbon support from Aldrich) was hydrogenated with H₂for 24 hours at room temperature (about 20° C. to about 25° C.) (andunder pressure, 63 psi). This form of Pd/C is used for catalysis, mainlyhydrogenations at described here. The metal (Pd) is distributed overfinely divided carbon making the surface area larger so that catalyst ismore reactive. The catalyst was filtered off, and the solvent wasevaporated off under vacuum to give 130.5 g of crude dihydrobromide ofjojoba diamine. The yield of pure product was 114.8 g (88%). The jojobadiamine (base) was obtained from the dihydrobromide by standard workup.The product was a white wax with a melting point of 40-45° C. The finalyield was 91.8 g (80%).

Reaction of Diaminojojoba with Epoxided Crystalline Resin in PhaseInversion Solvents followed by PIE

The coupling of the amine functionalized jojoba (diaminojojoba) to theepoxidized polyester resin may be done directly in the Methyl EthylKetone (MEK) and Isopropyl Alcohol (IPA) solvent mixture under inertatmosphere (nitrogen gas). About 150 grams of an epoxided crystallinepolyester resin, 52.5 grams of Methyl Ethyl Ketone (MEK), 43.5 grams ofIsopropyl alcohol (IPA) and 90 grams of diaminated jojoba oil wascharged into a 1 liter glass reaction vessel. The mixture was stirred atabout 80 rpm and heated to about 76° C. to substantially dissolve theresin in the solvent mixture and left to react for 24 hours under ablanket of nitrogen. After 24 hours, 4.53 grams of 10 wt % ammoniumhydroxide is added to the reaction vessel and the rpm is increased toabout 100 rpm. To this vessel was added 300 grams of hot DI water (96°C.—heated through coiled tube) at a rate of about 4.4 g/min. Then,another 150 grams of DI water is added at a rate of about 10 g/min. Oncecompleted the mixture was cooled to room temperature (about 20° C. toabout 25° C.) and screened through a 20 micron sieve. The resultingresin emulsion was comprised of about 30% solids by weight and had avolume average diameter of about 150 nanometers as measured with theNANOTRAC® particle size analyzer.

Synthesis of Toner Containing Chemically Bonded Jojoba Oil toCrystalline Polyester

A cyan polyester EA toner was prepared in a 2 L reactor (134.36 gramsdry theoretical toner); 137.1 grams amorphous emulsion (low molecularweight resin 23.3 wt % solids), 200.6 grams of the amorphous emulsion(high molecular weight resin; 16.0 wt % solids)—which is a 50:50 ratioof a high and low molecular weight resin, 35.14 grams of the jojobabound crystalline emulsion (crystalline polyester; 26 wt % solids), 1.01grams Dowfax 2A1 surfactant and 58.2 grams of the Pigment Cyan 15:3Dispersion were mixed together. While homogenizing the mixture at3000-4000 rpm an aluminum sulphate solution, consisting of 2.96 gramsaluminum sulphate with 36.6 grams of DI water was added over 20 minuteperiod. The slurry was then transferred to a 2 L Buchi where thetemperature was heated to begin aggregating at a batch temperature of43° C.

During aggregation, particle size measurements are taken and run in aMultisizer Coulter counter. Once at the targeted particle size a shellcomprised of the same amorphous emulsions in the core was added to thereactor and the reactor is further heated to achieve the final targetedparticle size. The slurry was then pH adjusted using sodium hydroxide(NaOH) and Versene-100 and the aggregation step was frozen at a pH ofabout 7.8. The method proceeds with the reactor temperature (Tr) beingincreased to 85° C. while maintaining a pH≧7.5 until Tr is 80 deg C.Once at 85° C. the pH of the toner slurry is adjusted to pH 7 with a pH5.7 Buffer. At which time the toner slurry is held to coalesce theparticles until they achieve the target circularity of ≧0.970 (about 40minutes). Once coalesced, the toner slurry was quench cooled. The finaltoner particle D50/GSDv/GSDn and circularity were about 5.85/1.21/1.22and 0978, respectively. The amount of CPE-bound jojoba oil in theparticle is calculated to be 6.8-wt %, of which 4.1% is the bound jojobaoil.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also, itwill be appreciated that various presently unforeseen or unanticipatedalternatives, modifications, variations or improvements therein may besubsequently made by those skilled in the art which are also intended tobe encompassed by the following claims. Unless specifically recited in aclaim, steps or components of claims should not be implied or importedfrom the specification or any other claims as to any particular order,number, position, size, shape, angle, color, or material.

What is claimed is:
 1. An emulsion aggregation toner particlecomprising: a bio-based oil chemically bonded to a polyester resin; anda colorant.
 2. The emulsion aggregation toner particle according toclaim 1, wherein the bio-based oil is a partially hydrogenated jojobaoil.
 3. The emulsion aggregation toner particle according to claim 1,wherein the toner particle has a core-shell structure, wherein the corecomprises a high molecular weight amorphous resin, a low molecularweight amorphous resin, and the bio-based oil chemically bonded to apolyester resin; and the shell comprises a high molecular weightamorphous resin and a lower molecular weight amorphous resin.
 4. Apolyester-wax resin emulsion comprising a bio-based oil chemicallybonded to a polyester resin.
 5. The emulsion aggregation toner particleaccording to claim 1, wherein the bio-based oil chemically bonded to apolyester resin is formed by a method comprising: epoxidizingunsaturated units of a polyester resin; synthesizing anamino-functionalized bio-based oil from a bio-based oil; and chemicallybonding the amino-functionalized bio-based oil to the epoxidized unitsof the polyester resin.
 6. The emulsion aggregation toner particleaccording to claim 5, wherein the method does not comprise a step ofproviding a second or separate wax emulsion.
 7. The emulsion aggregationtoner particle according to claim 1, wherein the bio-based oil isselected from the group consisting of a partially hydrogenated oilextracted from a plant, a non-hydrogenated vegetable oil extracted froma plant, and mixtures thereof.
 8. The emulsion aggregation tonerparticle according to claim 7, wherein the bio-based oil is a partiallyhydrogenated oil extracted from a plant.
 9. The emulsion aggregationtoner particle according to claim 5, wherein the amino-functionalizedbio-based oil is a diamino compound synthesized by a method comprising:functionalizing the bio-based oil with halogen atoms; forming a diazidefrom the halogen-functionalized bio-based oil; and hydrogenating thediazide.
 10. The emulsion aggregation toner particle according to claim5, wherein an epoxidizing agent containing a peroxide group is used toepoxidize the unsaturated units of the polyester resin.
 11. The emulsionaggregation toner particle according to claim 10, wherein theepoxidizing agent is a member selected from the group consisting ofmeta-chloroperoxybenzoic acid (MCPBA), peroxysulfuric acid, peroxyaceticacid, peroxytrifluoroacetic acid, O₂, O₃ (ozone), H₂O₂ (hydrogenperoxide), (CH₃)COOH (tert-butyl hydroperoxide), and magnesiummonoperoxyphthalate hexahydrate (MMPP).
 12. The emulsion aggregationtoner particle according to claim 10, wherein the peracid ismeta-chloroperoxybenzoic acid (MCPBA).
 13. The emulsion aggregationtoner particle according to claim 1, wherein the polyester resin isformed from unsaturated monomers and at least one of the unsaturatedmonomers is fumaric acid.
 14. The emulsion aggregation toner particleaccording to claim 1, wherein the polyester resin is a member selectedfrom the group consisting of poly(1,2-propylene-diethylene)terephthalte,polyethylene-terephthalate, polypropylene-terephthalate,polybutylene-terephthalate, polypentylene-terephthalate,polyhexylene-terephthalate, polyheptadene-terephthalate,polyoctalene-terephthalate, polyethylene-sebacate,polypropylene-sebacate, polybutylene-sebacate, polyethylene-adipate,polypropylene-adipate, polybutylene-adipate, polypentylene-adipate,polyhexylene-adipate polyheptadene-adipate, polyoctalene-adipate,polyethylene-glutarate, polypropylene-glutarate, polybutylene-glutarate,polypentylene-glutarate, polyhexylene-glutarate,polyheptadene-glutarate, polyoctalene-glutarate, polyethylene-pimelate,polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate,polyhexylene-pimelate, polyheptadene-pimelate, poly(propoxylatedbisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate),poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylatedbisphenol co-ethoxylated bisphenol co-fumarate), poly(1,2-propylenefumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylatedbisphenol co-maleate), poly(butyloxylated bisphenol co-maleate),poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate),poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate),poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenolco-itaconate), poly(co-propoxylated bisphenol co-ethoxylated bisphenolco-itaconate), poly(1,2-propylene itaconate), and mixtures thereof. 15.The emulsion aggregation toner particle according to claim 1, whereinthe bio-based oil is a member selected from the group consisting ofjojoba oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil,palm kernel oil, rapeseed oil, almond oil, cashew oil, hazelnut oil,peanut oil, macadamia oil, mongongo oil, pine nut oil, pistachio oil,walnut oil, bottle gourd oil, buffalo gourd oil, pumpkin seed oil,watermelon seed oil, acai oil, blackcurrant seed oil, borage seed oil,evening primrose oil, carob pod oil, amaranth oil, apricot oil, appleseed oil, argan oil, artichoke oil, avocado oil, babassu oil, ben oil,borneo tallow nut oil, cape chestnut oil, cocoa butter, algaroba oil,cocklebur oil, poppyseed oil, cohune oil, dika oil, false flax oil, flaxseed oil, soybean oil, sunflower oil, grape seed oil, hemp oil, kapokseed oil, lallemantia oil, marula oil, meadowfoam seed oil, mustard oil,nutmeg butter, nutmeg oil, okra seed oil, papaya seed oil, perilla seedoil, pequi oil, pine nut oil, poppyseed oil, prune kernel oil, quinoaoil, ramtil oil, rice bran oil, royle oil, sacha inchi oil, camelliaoil, thistle oil, tomato seed oil, wheat germ oil, tong oil, linseedoil, safflower oil, sesame oil, and combinations thereof.
 16. Theemulsion aggregation toner particle according to claim 1, wherein thebio-based oil comprises eicosenoic acids and alcohols in an amount offrom about 1% to about 30% by weight of the bio-based oil.
 17. Theemulsion aggregation toner particle according to claim 1, wherein thebio-based oil is present in an amount of from about 0.1% to about 25% byweight of the toner particles.
 18. The emulsion aggregation tonerparticle according to claim 5, wherein the polyester-wax resin emulsioncomprises about 30% solids by weight and has a volume average diameterof about 150 nanometers.
 19. The emulsion aggregation toner particleaccording to claim 5, wherein the method further comprises: forming apre-toner mixture comprising the polyester-wax resin emulsion;aggregating particles from the pre-toner mixture; halting theaggregating of the particles; and coalescing the particles to form tonerparticles.